JP6876124B2 - The catalyst and the process for producing fluorinated hydrocarbons using this catalyst - Google Patents

Description

The present invention relates to a catalyst, a method for preparing the catalyst, and a process using the catalyst. More specifically, the present invention relates to catalysts containing chroma and additional metals, as well as said catalysts in the addition or removal of halogens and hydrogen halides from / to compounds containing 2-3 carbon atoms. Regarding the process of using.

The enumeration or consideration of previously published literature within this specification should not necessarily be construed as a recognition that the literature is part of a state of the art or is common sense.

Halocarbon-based compounds, especially fluorocarbon-based compounds, are currently used in many commercial and industrial applications, such as propellants, foaming agents, and heat transfer fluids. Due to the demand for new refrigerants, there is increasing interest in and their use of fluorinated compounds as heat transfer fluids, especially (hydro) fluoroolefins.

(Hydro) haloalkenes, such as hydrofluoropropene, can be conveniently prepared from the corresponding hydro (halo) fluoroalkanes by dehalogenation hydrogenation. The conversion is carried out thermally, ie by pyrolysis, catalytically, by contacting the hydro (halo) fluoroalkane with the catalyst under suitable conditions, or chemically, typically with a hydro (halo) fluoroalkane. This can be done by contacting with a strong base such as an alkali metal hydroxide. Catalytic dehalogenation hydrogenation is considered preferred for commercial operation.

Hydrofluoropropene 1,1,1,2,3-pentafluoropropene (HFO-1225ye) is, for example, 1,1,1,2,3,3-hexafluoropropane in the gaseous state and trivalent chromium oxide or Partially fluorinated trivalent chromium oxide can be prepared optionally in the presence of oxygen (see US Pat. No. 5,679,875) by contact and defluorination hydrogenation.

Similarly, fluorination and / or hydrogen fluoride steps are also common in the process of producing (hydro) fluoroalkenes. Such a process can be carried out by contacting the HF with one or more (hydro) haloalkanes or (hydro) haloalkanes, preferably in the presence of a catalyst.

Despite the above processes, catalytic reactions involving halocarbons have many problems in use, one of which is that industrial scale processes make catalysts extremely hot and pressure, numerous regenerative and corrosive. Exposure to reagents. Those skilled in the art will know that the activity is steadily reduced over the life of the industrial catalyst and that the catalyst will eventually need to be replaced in an expensive procedure.

Therefore, there is a need for catalysts with improved stability over existing catalysts, as well as comparable or improved activity and selectivity.

In a first aspect, the invention provides a catalyst comprising rhodium and at least one additional metal or compound thereof, the catalyst having a total pore volume greater than ^{0.3 cm 3 / g and average fineness.} The pore diameter is 90 Å or more, the total pore volume is _{measured by the N 2} adsorption press-fit method, the average pore diameter is measured by the N ₂ BET press-fit method, and at least one additional metal is Li, Na, K, Ca, Mg, Cs, Sc, Al, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, It is selected from Pd, In, Pt, Cu, Ag, Au, Zn, La, Ce, and mixtures thereof.

A second aspect provides a method of producing 2,3,3,3-tetrafluoropropene (1234yf) from a saturated precursor in the presence of a catalyst as defined above.

This additional metal or compound thereof may also be referred to as a co-catalyst. Preferably, at least one additional metal is Li, Na, K, Ca, Mg, Cs, Cr, Zr, Nb, Pd, Ta, Zn, V, Mo, Ni, Co, In, Fe, Cu, And a mixture thereof, and even more preferably, the additional metal is zinc.

Those skilled in the art will appreciate that in catalysts, catalytic activity is generally understood to be proportional to the available surface area of the catalyst. Increasing the chances of the reagent interacting with the surface of the catalyst are expected to increase the rate of conversion.

However, in contrast to established teachings, we have surprisingly found that an increase in pore volume and average pore diameter, which can essentially reduce the surface area of the catalyst, is the stability and activity of the catalyst. Found to enhance both.

Without wishing to be bound by theory, this is the result of increased mass transfer through the catalyst, and this effect is believed to be more pronounced for _{C 3} compounds than for _{C 2 compounds.} Also, without wishing to be bound by theory, the wider pore diameters of the present invention allow the catalyst in use to produce (hydro) haloalkenes such as hydrofluoropropenes more quickly and effectively. Allows for a hole structure.

The pore structure of a solid porous material can be determined by several methods, one of the most commonly used is the BET theory (Brunauer) of multi-layer adsorption of condensed gas on a solid surface. , Emmett and Teller) -based _{adsorption and desorption of N 2} , and evaporation (desorption) of adsorbed gas during desorption. Nitrogen is a common adsorbent for scrutinizing micro and mesoporous regions. From the adsorption and desorption isotherms, the following can be calculated: the BET surface area from the adsorption of a single layer of _{N 2} , the total pore volume obtained from the amount of nitrogen adsorbed at ^{P / PO = 0.99, and the adsorption or} Average pore diameter that can be determined from desorption data using different calculations based on BET theory or BJH (Barrett, Joiner, and Hallenda) theory.

Preferably, the total pore volume of the catalyst, as measured by _{N 2} adsorption porosimetry, 0.35ccm ³ / g or 0.4 cm ³ / g or more, for example 0.45cm ³ /g,0.5cm ³ / g, is 0.55 cm ³ / g or even 0.6 cm ³ / g,.

_Preferably, as measured by N 2 BET adsorption porosimetry and an average pore width of the catalyst, 100 Å or more, for example 110Å more, or 120Å more.

_Preferably, as measured by N 2 BJH adsorption porosimetry and an average pore width of the catalyst, 130 Å or more, for example 140Å above, 150 Å or more, or 170Å more.

_Preferably, as measured by N 2 BJH desorption porosimetry and an average pore width of the catalyst, 90 Å or more, for example 100Å above, 110 Å or more, or 120Å more.

Preferably, the catalyst is provided in the form of one or more pellets containing the plurality of catalyst particles. Such catalyst particles can be pressed together, for example under load, to form pellets.

The pellet can contain one or more additional materials. For example, the pellet can contain graphite in an amount of preferably from about 0.5% to about 10% by weight, for example from about 1% to about 5% by weight.

Preferably, the pellet has a longest dimension of about 1 mm to about 100 mm. In some embodiments, the pellet may have a longest dimension of about 1 mm to about 10 mm, for example about 3 mm to about 5 mm.

Preferably, the catalyst is at least 80% by weight (eg, at least 85% by weight, at least 90% by weight, at least 92% by weight, at least 93% by weight, at least 94% by weight, at least 95% by weight, or at least 96% by weight) of chromia. including.

Advantageously, the catalyst may be a zinc / chromia catalyst. The term "zinc / chromium catalyst" means that the metal oxide catalyst comprises chromium, or a compound of chromium and zinc, or a compound of zinc.

The total amount of zinc or zinc compound present in the zinc / chromia catalyst of the present invention is typically about 0.01% to about 25, preferably 0.1% to about 25%, preferably 0. 01% to 6%, in some embodiments preferably 0.5% to about 25% by weight of the catalyst, preferably about 1-10% by weight of the catalyst, more preferably about 2-8% of the catalyst. By weight, for example about 4-6% by weight of the catalyst.

In a further preferred embodiment, the additional metal compound can include indium (eg, in _{the form of In 2} O ₃ ) and / or zirconium (eg, in the form of _{ZrO 2).}

Additional metals or compounds thereof are typically present in an amount of about 0.01 to about 25, preferably 0.1% to about 25, preferably 0.01 to 6% by weight of the catalyst, and some practices. In the form, preferably 0.5% to about 25% by weight of the catalyst, preferably about 1 to 10% by weight of the catalyst, more preferably about 2 to 8% by weight of the catalyst, for example about 4 to 6% by weight of the catalyst. Is.

In other embodiments, the catalyst may be an alumina catalyst having one or more co-catalysts selected from platinum, iron, chromium, and zinc. The total amount of co-catalyst is typically about 0.1 to about 60% by weight of the catalyst, preferably about 0.5 to about 50% by weight of the catalyst, for example 0.5% to about 25% by weight of the catalyst. Or about 1-10% by weight of the catalyst.

In such embodiments, the catalyst is at least 80% by weight (eg, at least 85% by weight, at least 90% by weight, at least 92% by weight, at least 93% by weight, at least 94% by weight, at least 95% by weight, or at least 96% by weight. ) Is preferably contained.

In some embodiments, the catalyst may be a fluorinated forms. For example, the catalyst may be fluorinated by treatment with HF at high temperatures.

Advantageously, the catalysts of the present invention are unused, i.e. novel. “Unused” means that the catalyst has not been contacted with any reagent, or has been placed under any pre-reaction conditions, and / or the catalyst has been used in advance to catalyze the reaction, or has been regenerated. It means that the catalyst has a total pore volume and an average pore diameter as described above, before it has been done.

The present invention also provides a method for preparing a catalyst, wherein the method is:
a) Steps to prepare metal salt solution and hydroxide solution,
b) A step of mixing the solution at a pH exceeding 7.5 to precipitate a metal hydroxide (s) and a step of precipitating the metal hydroxide (s).
c) The step of drying the precipitated metal hydroxide and
d) The step of calcining the metal hydroxide (s) to form the metal oxide (s) is included.

Preferably, the metal salt comprises a nitrate such as a hydroxide nitrate. In a preferred embodiment, the metal salt contains chromium and can include chromium nitrate salts such as _{Cr (OH) (NO 3} ) _2. The hydroxide solution can contain ammonium hydroxide (NH ₄ OH). Advantageously, step b) is carried out at a pH above 8. Preferably, step b) is performed at a pH of 8.1, 8.2, 8.3, 8.4, or 8.5 or higher.

In some embodiments, the metal salt solution is from about 1 mol / l to about 10 mol / l, such as about 2 mol / l to about 8 mol / l, such as about 3 mol / l to about 7 mol / l or about 4 mol / l to about 4 mol / l. It is provided at a concentration of 6 mol / l.

In some embodiments, the hydroxide solution is from 1 mol / l to about 10 mol / l, such as from about 2 mol / l to about 8 mol / l, such as from about 3 mol / l to about 7 mol / l or from about 4 mol / l to about 4 mol / l. It is provided at a concentration of 6 mol / l.

Preferably, step (b) is performed by mixing the solution in a solvent such as water. Alternative solvents can include alcohols, glycols, water mixtures, and other polar solvents.

Preferably, step b) is carried out at a substantially constant temperature, such as 0-50 ° C, preferably 10-30 ° C.

Preferably, step (b) is carried out with stirring the mixed solution. Such agitation can be provided by known suitable means such as impellers, jet mixers, recirculation pumps and the like.

The precipitate formed during step (b) preferably contains particles having an average longest dimension of about 5 μm to about 20 μm, such as about 7 μm to about 15 μm or about 8 μm to about 13 μm, such as about 10 μm. Such dimensions follow measurements by focused beam reflectance measurements.

Preferably, step (c) involves removing the liquid from the slurry of metal hydroxide precipitates (s) to produce a wet cake, for example by filtration or centrifugation. Such filtration can include the application of pressure differences across the filtration membrane. The cake can be washed, preferably by exposure to water (eg, deionized water) or alkaline aqueous solution (eg, ammonium hydroxide) prior to any drying or baking.

Preferably, step (c) involves removing a liquid, eg, a residual liquid, from the wet metal hydroxide (s) cake by exposing the cake to high temperatures. Such a high temperature may be, for example, 50 ° C. to 200 ° C., more preferably 80 ° C. to 150 ° C., for example, about 90 ° C. to about 120 ° C. The precipitate is preferably exposed to high temperatures for at least 15 minutes, for example at least 30 minutes or at least 1 hour. In certain embodiments, the precipitate can be exposed to high temperatures for more than 6 hours or more than 12 hours.

Step (d) preferably includes a step of firing the metal hydroxide after removing and / or drying the liquid. Such a firing step can include heating the metal hydroxide to a temperature of about 200 ° C. to about 550 ° C., such as about 250 ° C. to about 500 ° C., for example about 300 ° C. to about 400 ° C. Such a firing step can have a duration of about 5 minutes to about 12 hours. When heated to 400 ° C., sufficient to produce a catalyst with TGA ignition loss (LOI) at 400 ° C. of less than about 15%, such as less than about 12% or less than about 10%, for example about 8%. It is particularly preferable to perform firing over time.

The method preferably comprises mixing the calcined metal oxide with graphite to provide a catalyst composition comprising from about 0.1% by weight to about 10% by weight of graphite. In a preferred embodiment, the composition so formed can contain from about 0.5% to about 5% by weight graphite. Most preferably, the composition so formed contains from about 1% to about 3% by weight graphite.

In a preferred embodiment, the metal oxide and / or the catalyst composition can be pressed to form catalyst pellets. The pressing may be performed under a load of about 1-10 tons, for example about 5 tons. The pellets so formed can have a maximum dimension of about 1 mm to about 100 mm. In some embodiments, the pellet can have a longest dimension of about 1 mm to about 10 mm, for example about 3 mm to about 5 mm.

In an embodiment of a further aspect of the invention, _{a fluorination process for C 2-3} hydrohalocarbon species is provided, which process involves contacting the species with a catalyst according to the invention. This is typically done in the presence of HF. For the avoidance of doubt, _{the term C 2-3} hydrohalocarbons has a chain of two or three carbons and contains one or more hydrogen atoms and halogens (F, Cl, Br, I). Includes saturated or unsaturated compounds. In a preferred embodiment, hydrohalocarbon species comprises a C ₃ hydrohalocarbon species.

Examples of such processes include contacting trichloroethylene with a catalyst in the presence of HF to produce 1,1,1,2-tetrafluoroethane (134a), 1,1,1,2, Conversion of 3-pentachloropropane (240db) to 2-chloro-3,3,3-trifluoropropene (1233xf), 1,233xf of 2,3,3,3-tetrafluoropropene (1234yf) and / or 1,1 , 1,2,2-Pentafluoropropane (245cc) conversion, 1,1,1,3-tetrachloropropane (250fb) conversion to 3,3,3-trifluoropropene (1243zf), or 2, Includes conversion of 3-dichloro-1,1,1-trifluoropropane (243db) to 1233xf and / or 1234yf.

In another aspect of the present invention, C _{2 to 3} hydrohalocarbon species (preferably C ₃ hydrohalocarbon species) of dehydrohalogenation process is provided a process, contacting a seed and a catalyst, e.g. It involves contacting a hydro (halo) fluoropropane with a catalyst to produce a fluoropropene, preferably a tetrafluoropropene (1234) such as 1234ze ((E) or (Z)) or 1234yf. Advantageously, this is 245 cc and / or 1,1,1,2,3-pentafluoropropane (245 eb) 2,3,3,3-tetrafluoropropene (1234yf) and / or 1,3. , 3,3-Tetrafluoropropene (1234ze) conversion, 1,1,1,3,3-pentafluoropropane (245fa) conversion to 1234ze, or 1-chloro-1,3,3,3- Conversion of tetrafluoropropane to 1-chloro-3,3,3-trifluoropropene (1233zd) or 1234ze can be included.

A further aspect of the invention provides a process of removing HF or removing from saturated C _2-3 hydrohalocarbon species (preferably C ₃ hydrohalocarbon species), the process of which is the species and the catalyst according to the invention. Includes contact with.

In another aspect of the invention _{is provided a process of adding HF to unsaturated C 2-3} hydrohalocarbon species (preferably C ₃ hydrohalocarbon species), the process of combining the species with the catalyst according to the invention. Including contact.

The process described in the claims can be carried out in the liquid phase or the gas phase, but is preferably carried out in the gas phase. This process can be carried out at atmospheric pressure, quasi-atmospheric pressure, or ultra-atmospheric pressure, typically 0 to about 30 bara, preferably about 1 to about 20 bara, eg 15 bara.

Typically, the gas phase process of the present invention is carried out at a temperature of about 100 ° C. to about 500 ° C. (eg, about 150 ° C. to about 500 ° C. or about 100 ° C. to about 450 ° C.). Preferably, the process is carried out at a temperature of about 150 ° C. to about 450 ° C., such as about 150 ° C. to about 400 ° C., for example about 175 ° C. to about 300 ° C. Lower temperatures, such as about 150 ° C. to about 350 ° C., such as about 150 ° C. to about 300 ° C. or about 150 ° C. to about 250 ° C., can also be used in the conversion from 250 fb to 1243 zf.

The process typically involves about 1: 1 to about 100: 1, such as about 3: 1 to about 50: 1, such as about 4: 1 to about 30: 1, or about 5: 1 or 6: 1. Use a HF: organic molar ratio of ~ about 20: 1 or 30: 1.

The reaction time of this process is generally from about 1 second to about 100 hours, preferably from about 10 seconds to about 50 hours, such as from about 1 minute to about 10 or 20 hours. In a continuous process, the typical contact time between the catalyst and the reagent is about 1 to about 1000 seconds, such as about 1 to about 500 seconds, or about 1 to about 300 seconds, or about 1 to about 50, 100, or 200. Seconds.

The present invention is illustrated by the following non-limiting examples and illustrated by the following figures.

It is a graph which plotted the particle size distribution at the time point in the reaction of Comparative Example 8, and the weight value is not given in order to emphasize small particles. It is a graph which plotted the particle size distribution at the time point in the reaction of Comparative Example 8, and the weight value is given in order to emphasize a large particle. It is a plot graph of the particle size distribution at the time point during the reaction of Comparative Example 9, and no weighting value is given to emphasize small particles. It is a graph which plotted the particle size distribution at the time point in the reaction of Comparative Example 9, and the weight value is given in order to emphasize a large particle. It is a graph which plotted the particle size distribution at the time point during the reaction of Comparative Example 10, and the weight value is not given in order to emphasize small particles. It is a graph which plotted the particle size distribution at the time point in the reaction of Comparative Example 10, and the weight value is given in order to emphasize a large particle. It is a graph which plotted the particle size distribution at the time point during the reaction of Example 11, and the weight value is not given in order to emphasize a small particle. It is a graph which plotted the particle size distribution at the time point during the reaction of Example 11, and the weight value is given in order to emphasize a large particle. 6 is a graph plotting the presence of fine particles in the reactions of Examples and Comparative Examples 8 to 11. It is the graph which plotted the particle size distribution at the end of the reaction of Examples and Comparative Examples 8-11, and the weight value is not given in order to emphasize small particles. It is a graph which plotted the particle size distribution at the end of the reaction of Examples and Comparative Examples 8-11, and a weight value is given to emphasize a large particle.

The catalysts of Examples 1-7 were produced by the following methods:
500 mL of deionized water heel was added to a 1.7 L jacketed glass container equipped with an overflow, overhead stirrer, pH probe, and thermocouple and cooled to 15 ° C. The stirrer was operated at 500 rpm, stored in Example 5 and rotated at 250 rpm.

_{Zn (NO 3} ) in a 600 mL beaker ₂ . 6H ₂ O (19.03 g) was dissolved in a solution of _{Cr (NO 3} ) ₂ (OH) _{(aqueous solution) (500 g).} In another beaker, 500 g of a 17% NH ₄ OH solution was prepared.

The metal and ammonia solutions were pumped into the cooling water at 5 ml / min. Immediate precipitation of green / blue solids occurs. As shown in Table 1 below, the pH of the mixture was monitored and the flow rate of the reactants was adjusted to maintain the target pH of each example. The reaction was continued until all the metal solutions were added.

The slurry was filtered under vacuum until a filtered cake was formed and then washed 4 times with deionized water (eg "a") or dilute aqueous ammonia solution (eg "b").

The filtered cake was then dried in a standard oven at 105 ° C. overnight and then baked under flowing nitrogen (200 ml / min) at 300 ° C. for 12 hours to produce 6.5% ZnO / Cr ₂ O ₃ . The heating rate of the chamber furnace was set to 2 ° C./min. The mass loss rate during firing was recorded.

In a Waring blender, 2 wt% graphite was blended with the cooled calcination catalyst precursor and the resulting mixture was sieved to <250 μm. The sieved mixture was molded into pellets (3 g per pellet) under a load of 5 tonnes in a 32 mm pellet die.

The pellets were then ground to a mesh size of 0.5-1.4 mm for catalytic testing. Surface area, pore volume, and the size was measured by N ₂ adsorption / desorption porosimetry. The Zn content was measured by fluorescent X-ray spectroscopy. The results are shown in Table 1 together with the results for Comparative Example 1. The chromia catalyst had a specific surface area of ^{160-200 m 2} / g and a pore volume of more than ^{0.22 cm 3 / g.}

The data clearly show that an increase in the pH of the precipitate results in a significant increase in the pore volume of the precipitation catalyst.

The pelleted catalyst was tested for catalyst effectiveness in converting trichlorethylene to 134a. The atmospheric pressure screening device was equipped with four reaction tubes, each with an independent HF, organic matter, and nitrogen supply. The organic matter supply system was filled with trichlorethylene. Each reactor was loaded with 2 g of catalyst having a particle size in the range of 0.5-1.4 mm. First, a stream of nitrogen (60 ml / min) was directed at the reactor inlet and the catalyst was dried at 250 ° C. for 1 hour.

Following the catalyst drying operation, HF vapor is diluted with nitrogen (60 ml / min) at a flow rate of 30 ml / min and fed to each reactor, 250 on the catalyst until HF is observed off-gas in the reactor. It was allowed to pass at ° C. for about 30 minutes. At this point, the nitrogen stream (reduced to 30 ml / min) was redirected towards the reactor outlet. _{The catalyst was then exposed to a HF: N 2} (30: 5-ml / min) stream at 250 ° C. for an additional hour before raising the temperature to 450 ° C. at 40 ° C. per hour. These temperatures were maintained for 10 hours.

The reactor was first cooled to 350 ° C. and trichlorethylene was fed onto the catalyst at 10 ° C. via liquid trichlorethylene by sprayed nitrogen (8 ml / min). As a result, trichlorethylene gas having a flow rate of 0.5 ml / min was obtained. _{The catalyst was equilibrated in a HF: trichlorethylene: N 2} (30: 0.5: 10-ml / min) gas stream for about 2 hours before reducing the reactor temperature to 300 ° C. The catalyst was re-equilibrated for about 1 hour before measuring the formation of 133a and 134a from each. Temperature and yield were monitored throughout the reactor.

Next, the supply of organic matter was stopped, and the reactor temperature was raised to 490 ° C. at 40 ° C./hour while flowing 30 ml / min HF on the catalyst, which was held for 10 hours and cooled to 350 ° C. Then, trichlorethylene was prepared as described above. This process was repeated at a stress temperature of 514 ° C, 522 ° C for some examples.

The activity and stability results are shown as a comparison with the results of Comparative Example 1, which is a commercially available catalyst tested under the same conditions.

The activity is determined by calculation.
Activity = 50- (S2-RT)
In the formula, S2 is the predicted reaction temperature for obtaining a yield of 134a of 10% at the stress temperature of 2, and RT is 287.5 ° C.

Stability is determined by calculation.
Stability = 50- (S3-RT)
In the formula, S3 is the predicted reaction temperature for obtaining a yield of 134a of 10% at a stress temperature of 3, and RT is 287.5 ° C.

The results are shown in Table 2 below.

The results show a clear correlation between increased pore volume and width and increased stability and activity compared to prior art catalysts. This activity appears to persist even when the surface area is reduced compared to commercially available catalysts.

Comparative Examples 8, 9, and 10 and Example 11
Catalysts were prepared substantially according to the methods of Examples 1-8, adapted as described below with reference to Table 3.

A Mettler Toledo Optimax automated laboratory reactor was fitted with a focused beam reflection measurement (FBRM) G400 14 mm probe with overhead agitation and filled with 500 ml of deionized water heel.

The metal solution was pumped to the reactor at 5 ml / min. A 17% ammonium hydroxide solution was also added at 5 ml / min. The pH was carefully monitored and the flow rate of the reactants was changed to maintain the target pH. The reaction was continued until 300 g of metal solution was added. The particle size of the precipitate was monitored during the reaction using an FBRM G400 probe.

The resulting slurry was vacuum filtered and washed 3 times with deionized water. The filtered cake was dried at 110 ° C. and then baked under fluid nitrogen (200 ml / min) at 300 ° C. for 12 hours to produce Cr ₂ O ₃ and 6.5% Zn O _{/ Cr 2 O 3} . This was ground and mixed with 2% graphite before pelleting at 5 tonnes.

Comparative Example 8
Figures 1 and 2 and Table 4 show the measured particle size distributions 2, 6, and 15 minutes after the start of administration and after the completion of administration. Two minutes after the start, most of the particles are very small, but there are also some large particles. These large particles disappear 6 minutes after the start of administration, and by that time the total number of small particles is maximized. The distribution then shows a gradual shift to larger sizes.

Comparative Example 9
Figures 3 and 4 and Table 5 show the measured particle size distributions 2, 6, and 15 minutes after the start of administration and after the completion of administration. Most of the large particles are present 2 minutes after the start. However, in 6 minutes, the number of large particles decreased and the number of small particles increased significantly. The particle system shows little change during the last 15 minutes of administration.

Comparative Example 10
Figures 5 and 6 and Table 6 show the measured particle size distributions 2, 6, and 15 minutes after the start of administration and after the completion of administration. After 2 minutes from the start, the presence of small particles is predominant, which increases in number when reaching 6 minutes. After that, the total number of those small particles gradually decreases, and the number of large particles increases.

Example 11
7 and 8 and Table 7 show the measured particle size distributions 2, 6, and 15 minutes after the start of administration and after the completion of administration. The distribution indicates that the number of smaller particles gradually increases over the process of administration. During the last 15 minutes of administration, the number of larger particles is reduced.

FIG. 9 shows real-time data collection for the total number of microparticles (both less than 5 μm and 8 μm to 25 μm) for Comparative Examples 8 and 9. From this, the effects of flow turbulence or pH fluctuations could be seen immediately. It also demonstrates that leaving the final slurry agitated for extended periods of time did not affect particle size or distribution.

A comparison of the final particle size distributions of the slurries is shown in FIGS. 10 and 11 and Table 8. The results clearly show that increasing the pH of the precipitate has a significant effect on the total number of particles and particle size. Both experiments at pH 8.5 have smaller average sizes and smaller particles than those at pH 7.0. Changing the composition of the metal is also effective, but on a much smaller scale. Both experiments with zinc show a slightly smaller average size compared to the chromium-only counterpart.

The resulting dry calcined pellet catalyst was tested by N ₂ adsorption / desorption porosimetry were determined surface area, total pore volume, and average pore diameter. The results are shown in Table 8 below.

It is clear that the catalysts of Comparative Examples 8 and 10 (adjusted at pH 7) have a larger particle size, a larger BET surface area, a smaller pore diameter, and a smaller volume in the slurry. In contrast, the catalysts of Comparative Examples 9 and 11 (pH 8.5 adjusted) had a smaller particle size in the slurry, a smaller BET surface area, and a larger pore diameter, and a larger volume. Brought.

The catalysts of Comparative Examples 8, 9, and 10 and Example 11 were subjected to the same performance tests as in Examples 1-7. The results are shown in Table 9 below.

These results show the improvement in catalyst stability of Comparative Examples 9 and 11 as compared with Comparative Examples 8 and 10. This demonstrates that supporting larger pore diameters, larger pore volumes, and / or smaller precipitated particle diameters in the case of precipitation above the BET surface area results in improved performance in the catalyst. These parameters can be controlled by controlling the pH of the precipitate.

Preferences and options in a given aspect, feature, or parameter of the invention are combined with any and all preferences and options in all other aspects, features, and parameters of the invention, unless otherwise indicated in the context. It should be considered as disclosed.

Examples and Comparative Examples 12-23
The catalyst of the comparative example was prepared according to the following method. 20 500 mL of deionized water heel was added to a 1.7 L jacketed glass container equipped with an overflow, overhead stirrer, pH probe, and thermocouple and cooled to 15 ° C. The stirrer was operated at 500 rpm.

A solution (1036 g) of Cr (NO ₃ ) ₂ (OH) _{(aqueous solution)} was weighed in a 2000 mL beaker. In another beaker, 599 g of a 17% NH ₄ OH solution was prepared.

The metal and ammonia solutions were pumped into the cooling water at 5 ml / min. Immediate precipitation of green / blue solids occurs. The pH of the mixture was monitored and the flow rate of the reactants was adjusted to maintain the target pH of 8.5. The reaction was continued until all the metal solutions were added.

The chromium hydroxide slurry was divided into two parts, filtered separately under vacuum until a filtered cake was formed, then each was washed 3 times with deionized water (3 x 500 mL). The resulting filtered cake was mixed and then divided into four parts. A portion of the cake was then dried in a standard oven at 80 ° C. for 3 days to form the catalyst of Comparative Example 20. The remaining three were placed in a separate beaker (600 ml) containing 200 mL of deionized water with a magnetic stirring bar and mixed until the filtered cake was reslurried.

For Example 21, MoCl ₅ (1.08 g) was added to 20 ml of deionized water, the resulting solution was added to one of the beakers containing the chromium hydroxide slurry and stirred at room temperature for 2 hours.

Regarding Example 22, NiCl ₂ . 6H ₂ O (1.53 g) was added to 20 ml of deionized water, the resulting solution was added to one of the beakers containing the chromium hydroxide slurry and stirred at room temperature for 2 hours.

For Example 23, NbCl ₅ (1.10 g) was added to 20 ml of methanol, the resulting solution was added to one of the beakers containing the chromium hydroxide slurry, and the mixture was stirred at room temperature for 2 hours.

Next, each of the above slurries was dried in a standard oven at 80 ° C. for 3 days, and then calcined under flowing nitrogen (200 ml / min) at 300 ° C. for 12 hours to obtain metal oxide / Cr ₂ O ₃ (metal = Ni). , Nb, or Mo) was generated. The heating rate of the chamber furnace was set to 2 ° C./min. The mass loss rate during firing was recorded.

In a Waring blender, 2 wt% graphite was blended with the cooled calcination catalyst precursor and the resulting mixture was sieved to <250 μm. The sieved mixture was molded into pellets (3 g per pellet) under a load of 5 tonnes in a 32 mm pellet die.

The pellets were then ground to a mesh size of 0.5-1.4 mm for catalytic testing. Surface area, pore volume, and the size was measured by N ₂ adsorption / desorption porosimetry. The Ni, Mo, and Nb contents were measured by X-ray fluorescence spectroscopy.

The performance of these catalysts was tested for the formation of 1234yf from 243db fluorination and compared to the performance of commercially available Chromia catalysts (CE12-CE19) containing varying amounts of co-catalysts. The pore volume and diameter of each catalyst were also tested.

The atmospheric pressure screening device was equipped with four reaction tubes, each with an independent HF, organic matter, and nitrogen supply. The organic matter supply system was filled with 243db. Each reactor was filled with 2 ml of catalyst having a particle size in the range of 0.5-1.4 mm. First, a stream of nitrogen (60 ml / min) was directed at the reactor inlet and the catalyst was dried at 200 ° C. for 2 hours.

Following the catalyst drying operation, HF vapor is diluted with nitrogen (60 ml / min) at a flow rate of 30 ml / min and fed to each reactor, 300 on the catalyst until HF is observed off-gas in the reactor. It was allowed to pass at ° C for about 60 minutes. At this point, the nitrogen stream (reduced to 30 ml / min) was redirected towards the reactor outlet. The reactor temperature was raised to 360 ° C at 40 ° C. per hour. These temperatures were maintained for 10 hours.

The reactor was cooled to 350 ° C. and 243db was fed onto the catalyst at 10 ° C. via liquid 243db with spray nitrogen (4-6 ml / min). As a result, 243db gas having a flow rate of 0.5 to 1 ml / min was obtained. _{HF: 243db: N 2} (30: 0.5-1.0: 4-6 ml / min) before sampling the reactor off-gas into a glass burette using DI water for GC analysis for approximately 1 hour. ) Equilibrated in a gas stream. The results are shown in Table 10 below.

The results show a clear improvement in selectivity for 1234yf when the catalyst of the present invention is used. Moreover, the results show significant pore enlargement once the catalysts of the invention are used and are not desired to be bound by any theory, but it is high pore volume and average fineness in unused catalysts. The effect of providing the pore diameter can be amplified.

Example 24
500 mL of deionized water heel was added to a 1.7 L jacketed glass container equipped with an overflow, overhead stirrer, pH probe, and thermocouple and cooled to 15 ° C. The stirrer was operated at 500 rpm, stored in Example 5 and rotated at 250 rpm.

_{Zn (NO 3} ) in a 600 mL beaker ₂ . 6H ₂ O (19.03 g) was dissolved in a solution of _{Cr (NO 3} ) ₂ (OH) _{(aqueous solution) (500 g).} In another beaker, 500 g of a 17% NH ₄ OH solution was prepared.

The metal and ammonia solutions were pumped into the cooling water at 5 ml / min. Immediate precipitation of green / blue solids occurs. As shown in Table 1 below, the pH of the mixture was monitored and the flow rate of the reactants was adjusted to maintain the target pH of each example. The reaction was continued until all the metal solutions were added.

The slurry was filtered under vacuum until a filtered cake was formed and then washed 4 times with deionized water (eg "a") or dilute aqueous ammonia solution (eg "b").

The filtered cake was then dried in a standard oven at 105 ° C. overnight and then baked under flowing nitrogen (200 ml / min) at 300 ° C. for 12 hours to produce 6.5% ZnO / Cr ₂ O ₃ . The heating rate of the chamber furnace was set to 2 ° C./min. The mass loss rate during firing was recorded.

In a Waring blender, 2 wt% graphite was blended with the cooled calcination catalyst precursor and the resulting mixture was sieved to <250 μm. The sieved mixture was molded into pellets (3 g per pellet) under a load of 5 tonnes in a 32 mm pellet die.

The pellets were then ground to a mesh size of 0.5-1.4 mm for catalytic testing. Surface area, pore volume, and the size was measured by N ₂ adsorption / desorption porosimetry. The Zn content was measured by fluorescent X-ray spectroscopy.

Example 25
500 mL of deionized water heel was added to a 1.7 L jacketed glass container equipped with an overflow, overhead stirrer, pH probe, and thermocouple and cooled to 15 ° C. The stirrer was operated at 411 rpm. Weigh a solution (500 g) of Cr (NO ₃ ) ₂ (OH) _(aqueous solution) into a 600 mL beaker, and In (NO ₃ ) ₃ . 3H ₂ O (13.3 g) and 17% NH ₄ OH solution (318 g) were weighed into another beaker. The catalyst was then prepared at a target pH of 8.5 by the same procedure as in Example 24 and the slurry was washed with deionized water (3 x 600 mL).

Example 26
500 mL of deionized water heel was added to a 1.7 L jacketed glass container equipped with an overflow, overhead stirrer, pH probe, and thermocouple and cooled to 15 ° C. The stirrer was operated at 406 rpm. Weigh a solution (500 g) of Cr (NO ₃ ) ₂ (OH) _(aqueous solution) into a 600 mL beaker, and ZrOCl ₂ . A _{solution of 8H 2} O (13.6 g) in methanol (50 mL) and a 17% solution of NH ₄ OH (350 g) was weighed into another beaker. The catalyst was then prepared at a target pH of 8.5 by the same procedure as in Example 24 and the slurry was washed with deionized water (3 x 600 mL).

Production of 1234yf and 245cc from 1233xf The performance of the catalysts of Examples 24-26 was tested for the production of 1234yf and 245cc from fluorination of 1233xf by contact with HF. The results were compared with the results of a commercially available Chromia catalyst (Comparative Example 27) and a commercially available Zn-doped Chromia catalyst (Comparative Example 28).

Each catalyst (3 mL, 0.5-1.4 mm) was loaded into a 0.5 inch OD Inconel 625 reactor supported by an Inconel mesh. The catalyst was dried at 250 ° C. under fluid nitrogen at 60 mL / min for at least 2 hours prior to prefluorination. The HF vapor flowing at 30 ml / min was then passed over the catalyst at 250 ° C. for 1 hour with 30 ml / min of nitrogen. Nitrogen was then directed to the reactor outlet where pure HF passed over the catalyst and exited. The temperature was gradually raised to 380 ° C. and maintained for 10 hours. The temperature was then reduced to 350 ° C. and the HF flow was reduced to 25 mL / min. A co-supply of 1233xf (2-chloro-3,3,3-trifluoropropene) was supplied by its own vapor pressure and the flow was controlled to 1 mL / min through an orifice plate. Reactor off-gas was periodically sampled into deionized water from continuous operation for 0.5-7 hours and analyzed by GC to determine reaction progression. The results are shown in Table 11 below.

From the data in Table 11, it is clear that the addition of co-catalysts to the base chromia catalyst increased their activity as compared to the reference catalysts of Comparative Example 27 without co-catalysts. By increasing both the pore volume and the pore diameter and adding a zinc cocatalyst, it is comparable in activity to the catalyst of Comparative Example 28, but more selective and stable (Example 24). We were able to produce such a catalyst.

Production of 1234yf from 245cc The performance of the catalysts of Examples 24 and 25 was tested for the production of 1234yf from defluorinated hydrogenation of 245cc. The results were compared with the results of a commercially available chromia catalyst (Comparative Example 29) and a commercially available zinc-accelerated chromia catalyst (Comparative Example 30).

Each catalyst (3 mL, 0.5-1.4 mm) was loaded into a 0.5 inch OD Inconel 625 reactor supported by an Inconel mesh. The catalyst was dried at 250 ° C. under fluid nitrogen at 60 mL / min for at least 2 hours prior to prefluorination. The HF vapor flowing at 30 mL / min was then passed over the catalyst at 250 ° C. for 1 hour with 30 mL / min of nitrogen. Nitrogen was then directed to the reactor outlet where pure HF passed over the catalyst and exited. The temperature was gradually raised to 380 ° C. and maintained for 10 hours. The temperature was then reduced to 250 ° C. and the HF flow was reduced to 25 mL / min. A co-supply vapor of 245 cc (1,1,1,2,2-pentafluoropropane) was supplied at 9 ° C. via a liquid by sprayed nitrogen (1 mL / min) to obtain a 245 eb stream of 1 mL / min. .. Reactor off-gas was periodically sampled into deionized water from continuous operation for 0.5-7 hours and analyzed by GC to determine reaction progression. The results are shown in Table 12 below.

From the results shown in Table 12, it is clear that the catalytic activity is increased by promoting chromia with Zn and In. Increasing the pore volume and average pore diameter of Zn-accelerated chromia also increased the yield of 1234yf.

Production of 1234yf from 245eb The performance of the catalysts of Examples 24-26 was tested for the production of 1234yf and 245cc from defluorinated hydrogenation of 245eb. The results were compared with the results of a commercially available chromia catalyst (Comparative Example 31) and a commercially available zinc-accelerated chromia catalyst (Comparative Example 32).

Each catalyst (3 mL, 0.5-1.4 mm) was loaded into a 0.5 inch OD Inconel 625 reactor supported by an Inconel mesh. The catalyst was dried at 250 ° C. under fluid nitrogen at 60 mL / min for at least 2 hours prior to prefluorination. The HF vapor flowing at 30 mL / min was then passed over the catalyst at 250 ° C. for 1 hour with 30 mL / min of nitrogen. Nitrogen was then directed to the reactor outlet where pure HF passed over the catalyst and exited. The temperature was gradually raised to 380 ° C. and maintained for 10 hours. The temperature was then reduced to 250 ° C. and the HF flow was reduced to 25 mL / min. A co-supply vapor of 245 eb (1,1,1,2,3-pentafluoropropane) was supplied at 9 ° C. via a liquid by sprayed nitrogen (1 mL / min) to obtain a 245 eb stream of 1 mL / min. .. Reactor off-gas was periodically sampled into deionized water from continuous operation for 0.5-7 hours and analyzed by GC to determine reaction progression. The results are shown in Table 13.

As shown by the results in Table 13, increasing the pore volume and average pore diameter of Zn-accelerated chromia (Example 24) increased the selectivity to 1234yf. Similar facilitation with In and Zr, as well as increased pore volume and average pore diameter, also increased selectivity for 1234yf.

Preferences and options in a given aspect, feature, or parameter of the invention are combined with any and all preferences and options in all other aspects, features, and parameters of the invention, unless otherwise indicated in the context. It should be considered as disclosed.

Claims (76)

A catalyst for use in the fluorination and / or defluorination hydrogenation of hydrohalocarbon species, which comprises at least 80% by weight of chroma and at least one additional metal or compound thereof, wherein the catalyst is 0. It has a total pore volume of 4 cm ³ / g or more , an average pore diameter of 90 Å or more, the total pore volume is _{measured by the N 2} adsorption press-fitting method, and the average pore diameter is N ₂ BET adsorption press-fitting. A catalyst as measured by the method, wherein the at least one additional metal is selected from Zr, Nb, Mo, In, Zn, Mg, Al, Fe, Ni, Cu, and mixtures thereof. The catalyst according to claim 1 , wherein the total pore volume is 0.5 cm ³ / g or more. The catalyst according to claim 1 or 2 , wherein the average pore diameter of the catalyst is 100 Å or more when measured by the _{N 2 BET adsorption press-fitting method.} The catalyst according to claim 3 , wherein the average pore diameter of the catalyst is 110 Å or more or 120 Å or more when measured by the _{N 2 BET adsorption press-fitting method.} The catalyst according to any one of claims 1 to 4 , wherein the average pore diameter of the catalyst is 130 Å or more when measured by the _{N 2 BJH adsorption press-fitting method.} The catalyst according to claim 5 , wherein the average pore diameter of the catalyst is 140 Å or more, 150 Å or more, or 170 Å or more when measured by the _{N 2 BJH adsorption press-fitting method.} The catalyst according to any one of claims 1 to 6 , wherein the average pore diameter of the catalyst is 90 Å or more when measured by the _{N 2 BJH desorption press-fitting method.} The catalyst according to claim 7 , wherein the average pore diameter of the catalyst is 100 Å or more, 110 Å or more, or 120 Å or more when measured by the _{N 2 BJH desorption press-fitting method.} The catalyst according to any one of claims 1 to 8 , which is provided in the form of one or a plurality of pellets containing a plurality of catalyst particles. The catalyst according to claim 9 , wherein the pellet contains graphite in an amount of 0.5% by weight to 10% by weight. The catalyst according to claim 10 , wherein the pellets contain graphite in an amount of 1% to 5% by weight. The catalyst according to any one of claims 9 to 11 , wherein the pellet has a longest dimension of 1 mm to 100 mm. The catalyst according to any one of claims 1 to 12 , wherein the metal is a transition metal. 13. The catalyst according to claim 13, which comprises zinc. The catalyst according to any one of claims 1 to 14 , wherein the catalyst is an unused material. The method for preparing a catalyst according to any one of claims 1 to 15.
a) Steps to prepare metal salt solution and hydroxide solution,
b) A step of mixing the solution at a pH exceeding 8 to precipitate a metal hydroxide, and
c) The step of drying the precipitated metal hydroxide and
d) A method comprising a step of calcining the metal hydroxide to form a metal oxide. 16. The method of claim 16, wherein step b) is performed at a pH of 8.5 or higher. 16. The method of claim 16, wherein the metal salt comprises nitrate. The method of claim 18 , wherein the metal salt comprises a chromium nitrate. The method according to any one of claims 16 to 19 , wherein the hydroxide solution may contain _{ammonium hydroxide (NH 4 OH).} The method according to any one of claims 16 to 20 , wherein the metal salt solution is provided at a concentration of 1 mol / l to 10 mol / l. 21. The method of claim 21, wherein the metal salt solution is provided at a concentration of 2 mol / l to 8 mol / l. 22. The method of claim 22, wherein the metal salt solution is provided at a concentration of 3 mol / l to 7 mol / l or 4 mol / l to 6 mol / l. The method according to any one of claims 16 to 23, wherein the hydroxide solution is provided at a concentration of 1 mol / l to 10 mol / l. 24. The method of claim 24, wherein the hydroxide solution is provided at a concentration of 2 mol / l to 8 mol / l. 25. The method of claim 25 , wherein the hydroxide solution is provided at a concentration of 3 mol / l to 7 mol / l or 4 mol / l to 6 mol / l. The method according to any one of claims 16 to 26 , wherein step (b) is performed by mixing the solution in a solvent. The method according to any one of claims 16 to 27 , wherein step b) is performed at a substantially constant temperature of 0 to 50 ° C. 28. The method of claim 28 , wherein step b) is performed at a substantially constant temperature of 10-30 ° C. The method according to any one of claims 16 to 29 , wherein the step (b) is carried out while stirring the mixed solution. 30. The method of claim 30, wherein the mixing solution is agitated by the use of one or more impellers, jet mixers, or recirculation pumps. The method according to any one of claims 16 to 31 , wherein the precipitate formed in the step (b) contains particles having an average longest dimension of 5 μm to 20 μm. 32. The method of claim 32, wherein the precipitate formed during step (b) comprises particles having an average longest dimension of 7 μm to 15 μm or 8 μm to 13 μm. 33. The method of claim 33, wherein the precipitate formed during step (b) comprises particles having an average longest dimension of 10 μm. The method of any one of claims 16-34 , wherein step (c) comprises removing the liquid from the slurry of metal hydroxide precipitates to produce a wet cake. 35. The method of claim 35, wherein step (c) comprises removing the liquid from the slurry of metal hydroxide precipitates by filtration or centrifugation to produce a wet cake. 36. The method of claim 36, wherein the cake is washed prior to any drying or baking. 37. The method of claim 37, wherein the cake is washed by exposure to water or an aqueous alkaline solution prior to any drying or baking. Any of claims 35-38 , wherein step (c) comprises removing the liquid from the wet metal hydroxide cake by exposing the cake to a high temperature, wherein the high temperature is between 50 ° C and 200 ° C. The method described in paragraph 1. 39. The method of claim 39, wherein step (c) comprises removing the liquid from the wet metal hydroxide cake by exposing the cake to a high temperature, wherein the high temperature is between 80 ° C and 150 ° C. 40. The method of claim 40, wherein step (c) comprises removing the liquid from the wet metal hydroxide cake by exposing the cake to a high temperature, wherein the high temperature is between 90 ° C and 120 ° C. 41. The method of claim 41, wherein the precipitate is exposed to the high temperature for at least 15 minutes. 42. The method of claim 42, wherein the precipitate is exposed to the high temperature for at least 30 minutes or at least 1 hour. The method according to any one of claims 16 to 43 , wherein the step (d) includes a step of calcining the metal hydroxide. 44. The method of claim 44, wherein step (d) comprises firing the metal hydroxide after removing and / or drying the liquid. The method according to any one of claims 16 to 45, wherein the firing step comprises heating the metal hydroxide to a temperature of 200 ° C. to 550 ° C. 46. The method of claim 46, wherein the firing step comprises heating the metal hydroxide to a temperature of 250 ° C. to 500 ° C. 47. The method of claim 47, wherein the firing step comprises heating the metal hydroxide to a temperature of 300 ° C. to 400 ° C. The method of any one of claims 16-48 , wherein the calcination step is carried out over a period of time sufficient to produce a catalyst having a TGA ignition loss (LOI) of less than 15%. 49. The method of claim 49, wherein the calcination step is carried out over a period of time sufficient to produce a catalyst having a TGA ignition loss (LOI) of less than 12% or less than 10%. The method of claim 50 , wherein the calcination step is carried out over a period of time sufficient to produce a catalyst with 8% TGA ignition loss (LOI). The invention according to any one of claims 16 to 28 , further comprising mixing the calcined metal oxide with graphite to provide a catalyst composition containing 0.1% by weight to 10% by weight of graphite. Method. The method according to any one of claims 16 to 52 , wherein the calcined metal oxide is pressed to form a catalyst pellet. 52. The method of claim 52, wherein the catalyst composition is pressed to form catalyst pellets. 54. The method of claim 54, wherein the pressing is performed under a load of 1 to 100 tons. The method of claim 55 , wherein the pressing is performed under a load of 1-10 tons. 56. The method of claim 56, wherein the pellet so formed has a maximum dimension of 1 mm to 100 mm. 57. The method of claim 57, wherein the pellet so formed has a maximum dimension of 1 mm to 10 mm. 58. The method of claim 58, wherein the pellet so formed has a maximum dimension of 3 mm to 5 mm. A process for fluorinating a C _2-3 hydrohalocarbon species, comprising contacting the species with the catalyst according to any one of claims 1-15. The process of claim 60 , comprising contacting trichlorethylene with the catalyst in the presence of HF to produce 1,1,1,2-tetrafluoroethane (134a). The species is C ₃ hydrohalocarbon species The process of claim 60. A process for dehydrohalating and hydrogenating a C _2-3 hydrohalocarbon species, comprising contacting the species with the catalyst according to any one of claims 1-15. The species is C ₃ hydrohalocarbon species The process of claim 63. The process of claim 63 or 64 , comprising contacting the hydro (halo) fluoropropane with the catalyst to produce fluoropropene. 65. The process of claim 65, wherein the fluoropropene is tetrafluoropropene (1234). The hydro (halo) fluoropropane is 1,1,1,2,3-pentafluoropropane, 1,1,1,2,2-pentafluoropropane, and / or 1,1,1,3,3-. 65. The process of claim 65, comprising a compound selected from pentafluoropropane. The process of claim 66 , wherein the tetrafluoropropene comprises 1,3,3,3-tetrafluoropropene and / or 2,3,3,3-tetrafluoropropene. A process for producing tetrafluoropropene, which comprises contacting hydro (halo) propene with HF in the presence of the catalyst according to any one of claims 1-15. The process of claim 69 , wherein the hydro (halo) propene comprises hydrochlorofluoropropene. The process of claim 70 , wherein the hydrochlorofluoropropene is 1-chloro-3,3,3-trifluoropropene and / or 2-chloro-3,3,3-trifluoropropene. A process of removing HF from a saturated C _2-3 hydrohalocarbon species, comprising contacting the species with the catalyst according to any one of claims 1-15. A process of adding HF to unsaturated C _2-3 hydrohalocarbon species, comprising contacting the species with the catalyst according to any one of claims 1-15. The process according to any one of claims 61 to 73 , wherein the method is carried out in the gas phase. Use of the catalyst according to any one of claims 1 to 15 in the fluorination and / or defluorination hydrogenation of C _{2-3 hydrohalocarbon species.} The fluorinated catalyst according to any one of claims 1 to 15.

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